EP0010715B1 - N-alkyl-haloacetanilides substituted by an oxime group, processes for their preparation, herbicidal compositions containing them, a process for combating weeds, a process for preparing herbicidal compositions. - Google Patents

Description

The present invention relates to new oxime ethers, several processes for their preparation and their use as herbicides.

It has already become known that 2,6-diethyl-N-methoxymethylchloroacetanilide can be used for selective weed control (cf. R. Wegler, Chemistry of Plant Protection Products and Pest Control, Volume 5, page 255, Springer-Verlag (1977) and U.S. Patent 3,442,945). However, this compound is not always sufficiently effective and its selectivity is not always entirely satisfactory.

in welcher

• R' für Wasserstoff, Alkyl oder Alkoxy steht,
• R² für Wasserstoff, Alkyl, Alkoxy oder Halogen steht,
• R³ für Wasserstoff, Alkyl, Alkoxy oder Halogen steht,
• R⁴ für Wasserstoff oder Alkyl steht,
• R⁵ für Wasserstoff, Alkyl oder gegebenenfalls substituiertes Aryl steht,
• R⁶ für Wasserstoff, Alkyl, Alkenyl, Alkinyl, Alkoxyalkyl, Alkylthioalkyl, Dialkylaminoalkyl, Halogenalkyl, Alkoxycarbonylalkyl gegebenenfalls substituiertes Aryl oder gegebenenfalls substituiertes Aralkyl steht, und außerdem
  R⁵ und R⁶gemeinsam für eine Alkylen-Gruppe stehen, und
• Z für Halogen steht,

gefunden.There have now been new oxime ethers of the formula

in which

• R 'represents hydrogen, alkyl or alkoxy,
• R ^{2 represents} hydrogen, alkyl, alkoxy or halogen,
• R ^{3 represents} hydrogen, alkyl, alkoxy or halogen,
• R ^{4 represents} hydrogen or alkyl,
• R ^{5 represents} hydrogen, alkyl or optionally substituted aryl,
• R ^{6 represents} hydrogen, alkyl, alkenyl, alkynyl, alkoxyalkyl, alkylthioalkyl, dialkylaminoalkyl, haloalkyl, alkoxycarbonylalkyl optionally substituted aryl or optionally substituted aralkyl, and also
  R ⁵ and R ⁶ together represent an alkylene group, and
• Z represents halogen,

found.

The compounds of formula (I) can be in the syn or anti form; they are predominantly obtained as mixtures of both forms.

• a) Anilinomethyloxim-ether der Formel
  
  in welcher
  • R¹, R², R³, R⁴, R⁵ und R⁶ die oben angegebene Bedeutung haben,
  • mit Halogenessigsäurechloriden oder -bromiden bzw. -anhydriden der Formeln
    
    bzw.
    
    in welchen
  • Z die oben angegebene Bedeutung hat,
  • in Gegenwart eines Verdünnungsmittels und gegebenenfalls in Gegenwart eines Säurebindemittels umsetzt, oder
• b) Halogenacetanilide der Formel
  
  in welcher
  • R', R², R³ und Z die oben angegebene Bedeutung haben, mit substituierten Oxim-ethern der Formel
    
    in welcher
  • R⁴, R⁵ und R⁶ die oben angegebene Bedeutung haben, und
  • Y für Halogen, den Mesylat- oder Tosylat-Rest steht,
  • in Gegenwart eines Säurebinders und gegebenenfalls in Gegenwart eines Verdünnungsmittels umsetzt, oder
• c) N-substituierte Halogenacetanilide der Formel
  
  in welcher
  • R¹, R², R³, R⁴, R⁵ und Z die oben angegebene Bedeutung haben, mit Salzen von Hydroxylamin-(Derivaten) der Formel
    
    in welcher
  • R⁶ die oben angegebene Bedeutung hat,
  • in Gegenwart eines Verdünnungsmittels und in Gegenwart eines Säurebindemittels umsetzt, oder
• d) Alkalisalze von Oximen der Formel
  
  in welcher
  • R¹, R2, R³, R4, R5 und Z die oben angegebene Bedeutung haben, mit Halogeniden der Formel
    
    in welcher
  • ; R⁷ für Alkyl, Alkenyl, Alkinyl, Alkoxyalkyl, Alkylthioalkyl, Dialkylaminoalkyl, Halogenalkyl, Alkoxycarbonylalkyl, gegebenenfalls substituiertes Aryl oder gegebenenfalls substituiertes Aralkyl steht und
  • X für Chlor oder Brom steht,

in Gegenwart eines organischen Verdünnungsmittels oder in Gegenwart eines organisch-anorganischen Zweiphasensystems in Gegenwart eines Phasentransferkatalysators umsetzt, wobei die Alkalisalze der Oxime der Formel (VIII) in situ erzeugt werden.Furthermore, it was found that the oxime ethers of the formula (I) can be obtained if

• a) Anilinomethyloxime ether of the formula
  
  in which
  • R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ^{6 have} the meaning given above,
  • with haloacetic acid chlorides or bromides or anhydrides of the formulas
    
    respectively.
    
    in which
  • Z has the meaning given above,
  • in the presence of a diluent and optionally in the presence of an acid binder, or
• b) haloacetanilides of the formula
  
  in which
  • R ', R ² , R ³ and Z have the meaning given above, with substituted oxime ethers of the formula
    
    in which
  • R ⁴ , R ⁵ and R ^{6 have} the meaning given above, and
  • Y represents halogen, the mesylate or tosylate residue,
  • in the presence of an acid binder and optionally in the presence of a diluent, or
• c) N-substituted haloacetanilides of the formula
  
  in which
  • R ¹ , R ² , R ³ , R ⁴ , R ⁵ and Z have the meaning given above, with salts of hydroxylamine (derivatives) of the formula
    
    in which
  • R ^{6 has} the meaning given above,
  • in the presence of a diluent and in the presence of an acid binder, or
• d) alkali salts of oximes of the formula
  
  in which
  • R ¹ , R2, R ³ , R4, R5 and Z have the meaning given above, with halides of the formula
    
    in which
  • ; R ^{7 represents} alkyl, alkenyl, alkynyl, alkoxyalkyl, alkylthioalkyl, dialkylaminoalkyl, haloalkyl, alkoxycarbonylalkyl, optionally substituted aryl or optionally substituted aralkyl and
  • X represents chlorine or bromine,

in the presence of an organic diluent or in the presence of an organic-inorganic two-phase system in the presence of a phase transfer catalyst, the alkali metal salts of the oximes of the formula (VIII) being generated in situ.

The new oxime ethers of the formula (I) have strong herbicidal, in particular also selective herbicidal properties.

Surprisingly, the oxime ethers according to the invention show, with very good weed action, in particular better possibilities for use as a selective weed control agent in important crop plants than the 2,6-diethyl-N-methoxymethylchloroacetanilide known from the prior art, which is a highly active active ingredient of the same type of action. The substances according to the invention thus enrich the herbicidal compositions for selective weed control.

The oxime ethers according to the invention are generally defined by the formula (I). In the formula (I), R 'preferably represents hydrogen and straight-chain or branched alkyl and alkoxy each having 1 to 4 carbon atoms. R ² and R ³ are the same or different and are preferably hydrogen, straight-chain or branched alkyl and alkoxy each having 1 to 4 carbon atoms, and the halogens fluorine, chlorine and bromine. R ⁴ preferably represents hydrogen and straight-chain or branched alkyl having 1 to 4 carbon atoms. R ⁵ preferably represents hydrogen, straight-chain or branched alkyl having 1 to 4 carbon atoms, and optionally substituted aryl having 6 to 10 carbon atoms, such as in particular phenyl and naphthyl, where the following are preferred as substituents: halogen, straight-chain or branched alkyl having 1 up to 4 carbon atoms, haloalkyl with 1 to 2 carbon and 2 to 5 halogen atoms, fluorine and chlorine preferably being mentioned as halogens, alkoxy and alkylthio each with 1 or 2 carbon atoms, and cyano and nitro. R ⁶ preferably represents hydrogen, straight-chain or branched alkyl having 1 to 4 carbon atoms, alkenyl and alkynyl each having 2 to 4 carbon atoms, alkoxyalkyl and alkylthioalkyl each having 1 to 4 carbon atoms in the alkyl part and 1 to 4 carbon atoms in the alkoxy or in the alkylthio Part, dialkylaminoalkyl having 1 to 4 carbon atoms in each alkyl part, haloalkyl having 1 to 2 carbon and 1 to 5 halogen atoms, fluorine and chlorine preferably being mentioned as halogens, alkoxycarbonylalkyl having 1 to 4 carbon atoms in the alkyl part and 1 to 4 carbon atoms in the Alkoxy part, as well as for optionally substituted aryl and optionally substituted aralkyl having 6 to 10 carbon atoms in the aryl part and 1 to 2 carbon atoms in the alkyl part, such as in particular phenyl, naphthyl and benzyl, the preferred substituents being the aryl substituents already mentioned for R ⁵ come. R ⁶ and R ⁶ together also preferably represent a two- to four-membered alkylene group. Z preferably represents the halogens chlorine, bromine and iodine.

Those oxime ethers of the formula (I) in which R ', R ² and R ^{3 are} identical or different and for hydrogen, methyl, ethyl, isopropyl, sec-butyl, tert-butyl, methoxy, ethoxy or are very particularly preferred Are isopropoxy, R ² and R ³ also represent chlorine or bromine; R ^{4 represents} hydrogen, methyl or ethyl; R ^{5 represents} hydrogen, methyl, ethyl, isopropyl and phenyl or naphthyl which is optionally substituted by chlorine and / or methyl and / or methoxy and / or methylthio and / or trifluoromethyl; R ⁶ for hydrogen, methyl, ethyl, isopropyl, n-propyl, n-butyl, tert-butyl, vinyl, allyl, propargyl, methoxymethyl, ethoxymethyl, ethoxyethyl, methylthiomethyl, chloromethyl, chloroethyl, dimethylaminomethyl, ethyl-methylaminomethyl, diethylaminomethyl, Methoxycarbonylmethyl, optionally substituted by chlorine and / or methyl and / or methoxy and / or methylthio and / or trifluoromethyl, phenyl, naphthyl and benzyl; R ⁵ and R ⁶ also together represent the di- and trimethylene group; and Z represents chlorine or bromine.

In addition to the compounds mentioned in the preparation examples, the following compounds of the general formula (I) may be mentioned individually:

If 2,6-dimethylanilinomethyl methyl ketoximmethyl ether and chloroacetyl chloride are used as starting materials, the course of the reaction can be represented by the following formula (process variant a):

If 2-ethyl-6-methylchloroacetanilide and chloromethylaldoxime methyl ether are used as starting materials, the course of the reaction can be represented by the following formula (process variant b):

If 2,6-dimethyl-N-acetylmethyl-chloroacetanilide and O-methyl-hydroxylamine hydrochloride are used as starting materials, the course of the reaction can be represented by the following formula (process variant c):

If the sodium salt of 2,6-dimethyl-chloroacetanilidomethyl-methylketoxime and benzyl chloride are used as starting materials, the course of the reaction can be represented by the following formula (process variant d):

Formula (11) provides a general definition of the anilino-ketoxime ethers required as starting materials when carrying out process (a) according to the invention. In this formula, R ¹ to R ⁶ preferably represent those radicals which have already been mentioned for these radicals in connection with the description of the substances of the formula (I) according to the invention.

• e) Verbindungen der Formel (II) wenn man Aniline der Formel
  
  in welcher
  • R¹, R² und R³ die oben angegebene Bedeutung haben,
    • α) mit substituierten Oxim-ethern der Formel
      
      in welcher
      • R4, R⁵, R⁶ und Y die oben angegebene Bedeutung haben,
      
      in Gegenwart eines Säurebinders und gegebenenfalls in Gegenwart eines Verdünnungsmittels umsetzt, oder
    • ß) mit Propargylhalogeniden der Formel
      
      in welcher
      • R⁴ und Y die oben angegebene Bedeutung haben,
      
      in Gegenwart eines Säurebinders und gegebenenfalls in Gegenwart eines Verdünnungsmittels umsetzt, die entstehenden Propargyl-aniline der Formel
      
      in welcher
      • R¹, R², R³ und R⁴ die oben angegebene Bedeutung haben,
      
      in üblicher Weise hydratisiert und die entstehenden Anilin-Derivate der Formel
      
      in welcher
      • R', R², R³ und R⁴ die oben angegebene Bedeutung haben,
      
      mit Salzen von Hydroxylamin-(Derivaten) der Formel
      
      in welcher
      • R⁶ die oben angegebene Bedeutung hat,
      
      in Gegenwart eines Verdünnungsmittels und in Gegenwart eines Säurebindemittels umsetzt, oder
    • y) mit Keto-Derivaten der Formel
      
      in welcher
      • R⁴, R⁵ und Y die oben angegebene Bedeutung haben,
      
      in Gegenwart eines Säurebinders und gegebenenfalls in Gegenwart eines Verdünnungsmittels umsetzt, und die entstehenden substituierten Anilin-Derivate der Formel
      
      in welcher
      • R¹, R2, R3, R4 und R5 die oben angegebene Bedeutung haben, mit Salzen von Hydroxylamin-(Derivaten) der Formel
        
        in welcher
      • R⁶ die oben angegebene Bedeutung hat,
      
      in Gegenwart eines Verdünnungsmittels und in Gegenwart eines Säurebindemittels umsetzt. oder
• f) diejenigen Verbindungen der Formel (II), in denen R⁶ nicht für Wasserstoff steht, wenn man Anilin-Derivate der Formel
  
  in welcher
  • R¹, R2, R³, R⁴ und R⁵ die oben angegebene Bedeutung haben,
  
  mit Salzen des Hydroxylamins in Gegenwart eines Verdünnungsmittels und in Gegenwart eines Säurebindemittels umsetzt und die dabei entstehenden Oxime der Formel
  
  in welcher
  • R', R2, R³, R⁴ und R⁵ die oben angegebene Bedeutung haben,
  
  in Form ihrer Alkali-Salze mit Dimethylsulfat oder mit Halogeniden der Formel
  
  in welcher
  • R⁷ und X die oben angegebene Bdeutung haben,

in Gegenwart eines organischen Verdünnungsmittels oder in Gegenwart eines organisch-anorganischen Zweiphasensystems in Gegenwart eines Phasentransferkatalysators umsetzt, wobei die Alkalisalze der Oxime der Formel (XVI) in situ erzeugt werden.The anilinomethyloxime ethers of the formula (II) are not yet known. You get

• e) compounds of the formula (II) when anilines of the formula
  
  in which
  • R ¹ , R ² and R ^{3 have} the meaning given above,
    • α) with substituted oxime ethers of the formula
      
      in which
      • R4, R ⁵ , R ⁶ and Y have the meaning given above,
      
      in the presence of an acid binder and optionally in the presence of a diluent, or
    • ß) with propargyl halides of the formula
      
      in which
      • R ⁴ and Y have the meaning given above,
      
      in the presence of an acid binder and optionally in the presence of a diluent, the resulting propargyl anilines of the formula
      
      in which
      • R ¹ , R ² , R ³ and R ^{4 have} the meaning given above,
      
      hydrated in the usual way and the resulting aniline derivatives of the formula
      
      in which
      • R ', R ² , R ³ and R ^{4 have} the meaning given above,
      
      with salts of hydroxylamine (derivatives) of the formula
      
      in which
      • R ^{6 has} the meaning given above,
      
      in the presence of a diluent and in the presence of an acid binder, or
    • y) with keto derivatives of the formula
      
      in which
      • R ⁴ , R ⁵ and Y have the meaning given above,
      
      in the presence of an acid binder and optionally in the presence of a diluent, and the resulting substituted aniline derivatives of the formula
      
      in which
      • R ¹ , R2, R3, R4 and R5 have the meaning given above, with salts of hydroxylamine (derivatives) of the formula
        
        in which
      • R ^{6 has} the meaning given above,
      
      in the presence of a diluent and in the presence of an acid binder. or
• f) those compounds of formula (II) in which R ^{6 is} not hydrogen if aniline derivatives of the formula
  
  in which
  • R ¹ , R2, R ³ , R ⁴ and R ^{5 have} the meaning given above,
  
  with salts of hydroxylamine in the presence of a diluent and in the presence of an acid binder and the resulting oximes of the formula
  
  in which
  • R ', R2, R ³ , R ⁴ and R ^{5 have} the meaning given above,
  
  in the form of their alkali salts with dimethyl sulfate or with halides of the formula
  
  in which
  • R ⁷ and X have the meaning given above,

in the presence of an organic diluent or in the presence of an organic-inorganic two-phase system in the presence of a phase transfer catalyst, the alkali metal salts of the oximes of the formula (XVI) being generated in situ.

• Anilin; 2-Methylanilin; 2-Ethylanilin; 2-Isopropylanilin; 2-sek.-Butylanilin; 2-tert.-Butylanilin; 2,6-Dimethylanilin; 2,3-Dimethylanilin; 2,5-Dimethylanilin; 2,6-Diethylanilin; 2-Ethyl-6-methylanilin; 2,4,6-Trimethylanilin; 2-Ethyl-4,6-dimethylanilin; 2,6-Diethyl-4-methylanilin; 2,6-Diisopropyl-4-methylanilin; 2,3,6-Trimethylanilin; 2-Methyl-6-chloranlin; 2-tert.-Butyl-6-chloranilin; 2-Methoxy-6-methylanilin; 2,6-Dimethoxyanilin; 2-Methoxy-6-ethylanilin; 2,6-Diethoxyanilin.

The anilines of the formula (X) required as starting materials in the preparation of the anilinomethyloxime ethers of the formula (11) are generally known compounds of organic chemistry. Examples include:

• Aniline; 2-methylaniline; 2-ethylaniline; 2-isopropylaniline; 2-sec-butylaniline; 2-tert-butylaniline; 2,6-dimethylaniline; 2,3-dimethylaniline; 2,5-dimethylaniline; 2,6-diethylaniline; 2-ethyl-6-methylaniline; 2,4,6-trimethylaniline; 2-ethyl-4,6-dimethylaniline; 2,6-diethyl-4-methylaniline; 2,6-diisopropyl-4-methylaniline; 2,3,6-trimethylaniline; 2-methyl-6-chloroanlin; 2-tert-butyl-6-chloroaniline; 2-methoxy-6-methylaniline; 2,6-dimethoxyaniline; 2-methoxy-6-ethylaniline; 2,6-diethoxyaniline.

The substituted oxime ethers of the formula (V) which are furthermore required as starting materials in the preparation of the anilinomethyloxime ethers of the formula (11) by process (e) (variant α) are known (cf., for example, US Pat. No. 3,896,189); likewise the propargyl halides of the formula (XI) required for process (e), variant (β) (cf. Houben-Weyl, Methods of Organic Chemistry, Volume V / 3 and 4); as well as the keto derivatives of the formula (XIV) required for process (e), variant (y) (see Houben-Weyl, Methods of Organic Chemistry, Volume VII / 2 a, b, c) and the hydroxylamine ( Derivatives) of the formula (VII) (cf. Houben-Weyl, Methods of Organic Chemistry, Volume X / 1); or the respective compounds can be easily prepared by the processes indicated in the references mentioned.

In the preparation of the anilinomethyloxime ethers of the formula (11) by process (e), variants (a), (β) and (y), all customary acid acceptors can be used as acid binders. Alkali metal carbonates, such as potassium or sodium carbonate, are preferred.

All customary inert organic solvents can be used as diluents in process (e), variants (α), (β) and (y). Aromatic solvents, such as in particular toluene, and dimethylformamide are preferred. In the second stage of process (e), variant (y), alcohols, such as, in particular, methanol, are preferably used as solvents.

The reaction temperatures in process (e), variants (α), (β) and (y) can be varied within a substantial range. Generally one works between 0 ° C and 180 ° C, preferably between 20 ° C and 160 ° C.

In the reaction according to process (e), variants (α), (β) and (y), it is preferred to work with equimolar amounts. However, it is also possible to use one of the components, preferably the aniline of the formula (X), in excess. The reaction products are worked up and isolated by customary methods.

The oximes of the formula (XVI) required as starting materials in carrying out process (f) have hitherto not been known. However, they can be produced in a simple manner by process (e), variant (y).

Formula (IX) provides a general definition of the halides also required as starting materials in process (f). In this formula, R ⁷ and X preferably have those meanings which are preferably mentioned in connection with the description of process (d) according to the invention for these radicals.

In process (f), all inert organic solvents are suitable as diluents. These preferably include ethers such as diethyl ether and dioxane; aromatic hydrocarbons such as toluene and benzene; in some cases also chlorinated hydrocarbons, such as chloroform, Methylene chloride and carbon tetrachloride; and hexamethylphosphoric triamide.

The reaction temperatures can be varied within a substantial range when carrying out process (f). In general, one works between 20 and 150 ° C, preferably at room temperature. In individual cases it is advantageous to work at the boiling point of the solvent, for example between 60 and 100 ° C.

When carrying out process (f), 1 to 3 mol of halogen of the formula (IX) are preferably used per 1 mol of alkali metal salt of an oxime of the formula (XVI). The reaction products are worked up and isolated by customary methods.

In a preferred embodiment of process (f), the procedure is expediently started from an oxime of the formula (XVI), the latter converted into the salt in a suitable inert organic solvent by means of alkali metal hydride or amide, and the latter immediately without isolation reacted with a halide of the formula (IV), the compounds of the formula (11) being obtained in one operation with the emergence of alkali halide.

According to a further preferred embodiment of process (f), the preparation of the salts of the oximes of the formula (XVI) and the reaction in a two-phase system, such as, for example, aqueous sodium hydroxide solution and potassium hydroxide solution / toluene or methylene chloride, are expediently added with 0.01-1 Mol of a phase transfer catalyst, such as ammonium or phosphonium compounds.

The haloacetic acid chlorides and bromides or anhydrides of the formulas (IIla) and (IIIb) to be used as starting materials for process (a) according to the invention are generally known compounds of organic chemistry. Examples include: chloroacetyl chloride, bromoacetyl chloride, iodoacetyl chloride and the corresponding bromides and anhydrides.

Formula (IV) provides a general definition of the haloacetanilides required as starting materials when carrying out process (b) according to the invention. In this formula, R ', R ² , R3 and Z preferably represent those radicals which have already been mentioned for these radicals in connection with the description of the substances of the formula (I) according to the invention.

The haloacetanilides of the formula (IV) are generally known or they can be obtained in a generally known manner by appropriate anilines with a haloacetic acid chloride or bromide or anhydride of the formulas (Illa) or (Illb) in the presence of a inert organic solvent, such as toluene or dimethylformamide, optionally in the presence of an acid binder, such as. As potassium carbonate or triethylamine, at temperatures between 0 and 100 ° C. The chloro- and bromoacetanilides of the above-mentioned anilines of the formula (X) may be mentioned as examples.

Formula (V) provides a general definition of the substituted oxime ethers to be used as starting materials for process (b) according to the invention. In this formula, R ⁴ , R ⁵ and R ⁶ preferably represent those radicals which have already been mentioned in connection with the description of the substances of the formula (I) according to the invention. Y preferably represents chlorine, bromine, the mesylate and tosylate radical.

The substituted oxime ethers of the formula (V) are known (cf., for example, US Pat. No. 3,896,189); or can be obtained in a generally known manner by appropriate carbonyl compounds with hydroxylamine (derivatives) in the presence of a solvent, preferably an alcohol or an aqueous alcohol, at temperatures between 20 ° C and 100 ° C, preferably between 50 ° C and 80 ° C implemented. The hydroxylamine (derivative) is preferably used in the form of a salt, in particular as a hydrochloride, optionally in the presence of an acid binder, such as sodium acetate. The end products are isolated in the customary manner.

Formula (VI) provides a general definition of the N-substituted haloacetanilides required as starting materials when carrying out process (c) according to the invention. In this formula, R ', R ² , R ³ , R ⁴ R ⁵ and Z preferably represent those radicals which have already been mentioned as preferred in connection with the description of the substances of the formula (I) according to the invention.

• g) Halogenacetanilide der Formel
  
  in welcher
  • R', R², R³ und Z die oben angegebene Bedeutung haben,
    • α) mit Keto-Derivaten der Formel
      
      in welcher
      • R⁴, R⁵ und Y die oben angegebene Bedeutung haben,
      
      in Gegenwart eines Säurebinders und gegebenenfalls in Gegenwart eines Verdünnungsmittels umsetzt, oder
    • ß) mit Propargylhalogeniden der Formel
      
      in welcher
      • R⁴ und Y die oben angegebene Bedeutung haben,
      
      in Gegenwart eines Säurebinders und gegebenenfalls in Gegenwart eines Verdünnungsmittels umsetzt und die entstehenden Propargyl-halogenide der Formel
      
      in welcher
      • R¹, R², R³, R⁴ und Y die oben angegebene Bedeutung haben,
      
      in üblicher Weise hydratisiert, oder
• h) Anilin-Derivate der Formel
  
  in welcher
  • R', R², R³, R⁴ und R⁵ die oben angegebene Bedeutung haben,
  • mit bekannten Halogenessigsäurechloriden oder -bromiden der Formel
    
    in welcher
  • Z die oben angegebene Bedeutung hat,
  • in Gegenwart eines Verdünnungsmittels und gegebenenfalls in Gegenwart eines Säurebindemittels umsetzt.

Some of the N-substituted haloacetanilides of the formula (VI) are known (DE-OS 2 726 253). They can be produced in a simple manner using several processes. This gives N-substituted haloacetanilides of the formula (VI) if one

• g) haloacetanilides of the formula
  
  in which
  • R ', R ² , R ³ and Z have the meaning given above,
    • α) with keto derivatives of the formula
      
      in which
      • R ⁴ , R ⁵ and Y have the meaning given above,
      
      in the presence of an acid binder and optionally in the presence of a diluent, or
    • ß) with propargyl halides of the formula
      
      in which
      • R ⁴ and Y have the meaning given above,
      
      in the presence of an acid binder and optionally in the presence of a diluent and the resulting propargyl halides of the formula
      
      in which
      • R ¹ , R ² , R ³ , R ⁴ and Y have the meaning given above,
      
      hydrated in the usual way, or
• h) aniline derivatives of the formula
  
  in which
  • R ', R ² , R ³ , R ⁴ and R ^{5 have} the meaning given above,
  • with known haloacetic acid chlorides or bromides of the formula
    
    in which
  • Z has the meaning given above,
  • in the presence of a diluent and, if appropriate, in the presence of an acid binder.

The aniline derivatives of the formula (XV) required as starting materials in the preparation of the N-substituted haloacetanilides of the formula (VI) can be obtained in accordance with process (e), variant (y, first stage).

In the preparation of the N-substituted haloacetanilides of the formula (VI) by processes (g) and (h), all customary acid acceptors can be used as acid binders. Alkali metal carbonates, such as potassium or sodium carbonate, are preferred.

All customary inert organic solvents can be used as diluents in processes (g), variants (a) and (β) and (h). Aromatic solvents, such as in particular toluene, and dimethylformamide are preferred.

According to a preferred embodiment, the reaction according to process (h) is carried out in a two-phase system, such as, for example, aqueous sodium hydroxide solution or potassium hydroxide solution / toluene or methylene chloride, optionally with the addition of 0.1-1 mol of a phase transfer catalyst, such as, for example, an ammonium or phosphonium compound.

The reaction temperatures can be varied within a substantial range in processes (g), variants (a) and (β) and (h). Generally one works between 0 ° C and 180 ° C, preferably between 20 ° C and 160 ° C.

In the reaction according to process (g), variants (a) and (ß) and process (h), it is preferred to work with equimolar amounts. The reaction products are worked up and isolated by customary methods.

Formula (VII) provides a general definition of the hydroxylamine (derivatives) to be used as starting materials (in the form of their salts) for process (c) according to the invention. In this formula, R ⁶ preferably represents those radicals which have already been mentioned as preferred in connection with the description of the substances of the formula (I) according to the invention. The compounds of formula (VII) are preferably used in the form of their hydrohalides, in particular as the hydrochloride.

Formula (IX) provides a general definition of the halides required as starting materials when carrying out process (d) according to the invention. In this formula, R ⁷ preferably represents straight-chain or branched alkyl having 1 to 4 carbon atoms, alkenyl and alkynyl each having 2 to 4 carbon atoms, alkoxyalkyl and alkylthioalkyl each having 1 to 4 carbon atoms in the alkyl part and 1 to 4 carbon atoms in the alkoxy or im Alkylthio part, dialkylaminoalkyl with 1 to 4 carbon atoms in each alkyl part, haloalkyl with 1 to 2 carbon atoms and 1 to 5 halogen atoms, where halogen and fluorine and chlorine are preferably mentioned, alkoxycarbonylalkyl with 1 to 4 carbon atoms in the alkyl part and 1 to 4 carbon atoms in the Alkoxy part, as well as for optionally substituted aryl and optionally substituted aralkyl each having 6 to 10 carbon atoms in the aryl part and 1 to 2 carbon atoms in the alkyl part, phenyl, naphthyl and benzyl being specifically mentioned as aryl or aralkyl radicals, and as substituents preferably those in R. ⁵ aryl substituents already preferably mentioned come.

The hydroxylamine (derivatives) of the formula (VII) and the halides of the formula (IX) are generally known compounds of organic chemistry. _i

Suitable diluents for the reaction according to the invention in process (a) are preferably inert organic solvents. These preferably include ketones, such as diethyl ketone, in particular acetone and methyl ethyl ketone; Nitriles, such as propionitrile, especially acetonitrile; Ethers such as tetrahydrofuran or dioxane; aliphatic and aromatic hydrocarbons, such as petroleum ether, benzene, toluene or xylene; halogenated hydrocarbons, such as methylene chloride, carbon tetrachloride, chloroform or chlorobenzene; and esters, such as ethyl acetate.

Process (a) according to the invention can optionally be carried out in the presence of acid binders (hydrogen halide acceptors). All conventional acid binders can be used as such. These preferably include organic bases, such as tertiary amines, for example triethylamine or pyridine, furthermore inorganic bases, such as, for example, alkali metal hydroxides and alkali metal carbonates.

The reaction temperatures can be varied within a substantial range when carrying out process (a) according to the invention. Generally one works between 0 ° C and 120 ° C, preferably between 0 and 100 ° C.

When carrying out process (a) according to the invention, 1 to 1.5 mol of haloacetylating agent and 1 to 1.5 mol of acid binder are preferably employed per mol of the compounds of the formula (11). The compounds of the formula (I) are isolated in a customary manner.

Suitable diluents for the reaction according to the invention in process (b) are preferably inert organic solvents. These preferably include the solvents already mentioned in process (a).

The acid binders used in process (b) are preferably the substances already mentioned in process (a).

The reaction temperatures can be varied within a substantial range when carrying out process (b) according to the invention. Generally one works between 0 ° C and 150 ° C, preferably between 20 ° C and 100 ° C.

When carrying out process (b) according to the invention, preference is given to working with equimolar amounts. However, it is also possible to use one of the components in excess. The reaction products are worked up and isolated by customary methods.

In a preferred embodiment, the reaction according to process (b) is carried out in a two-phase system, such as, for example, aqueous sodium hydroxide solution or potassium hydroxide solution / toluene or methylene chloride, optionally with the addition of 0.1-1 mol of a phase transfer catalyst, such as, for example, an ammonium - or phosphonium compound, for example, be benzyl dode cyl-dimethyl-ammonium chloride (Zephirol) and triethyl-benzyl-ammonium chloride called, carried out (see also the preparation examples).

Suitable diluents for the reaction according to the invention in process (c) are preferably alcohols or aqueous alcohols.

Since the compounds of the formula (VII) are used in the form of their salts, preferably as hydrochlorides, when carrying out process (c), the process is carried out in the presence of an acid binder. These preferably include alkali carbonates and acetates.

The reaction temperatures can be varied over a wide range when carrying out process (c) according to the invention. Generally one works between 20 and 120 ° C, preferably between 40 ° C and 100 ° C.

When carrying out process (c) according to the invention, preference is given to working with equimolar amounts. However, it is also possible to use one of the components in excess. The reaction products are worked up and isolated by customary methods.

Suitable diluents for the reaction according to the invention in process (d) are all inert organic solvents. These preferably include ethers such as diethyl ether and dioxane; aromatic hydrocarbons such as toluene and benzene; in some cases also chlorinated hydrocarbons, such as chloroform, methylene chloride and carbon tetrachloride; and hexamethylphosphoric acid triamide.

The reaction temp _! doors can be varied in a larger range when carrying out process (d) according to the invention. In general, one works between 20 and 150 ° C, preferably at room temperature. In individual cases it is advantageous to work at the boiling point of the solvent, for example between 60 and 100 ° C.

When carrying out process (d) according to the invention, 1 to 3 mol of halide of the formula (IX) are preferably used per 1 mol of alkali metal salt of an oxime of the formula (VIII). The reaction products are worked up and isolated by customary methods.

In a preferred embodiment of process (d), the procedure is advantageously carried out by starting from an oxime of the formula (VIII), converting the latter into the salt in a suitable inert organic solvent by means of alkali metal hydride or amide, and the latter immediately without isolation reacted with a halide of the formula (IV), the compounds of the formula (I) according to the invention being obtained in one operation with the emergence of alkali halide.

According to a further preferred embodiment of process (d), the preparation of the salts of the oximes of the formula (VIII) and the reaction according to the invention are advantageously carried out in a two-phase system, such as, for example, aqueous sodium hydroxide solution and potassium hydroxide solution / toluene or methylene chloride, with the addition of 0.01- 1 mole of a phase transfer catalyst, such as an ammonium or phosphonium compound.

The active compounds according to the invention influence plant growth and can therefore be used as defoliants, desiccants, haulm killers, germ inhibitors and in particular as weed killers. Weeds in the broadest sense are understood to mean all plants that grow up in places where they are undesirable. Whether the substances according to the invention act as total or selective herbicides depends essentially on the amount used.

• Dikotyle Unkräuter der Gattungen:
  Sinapis, Lepidium, Galium, Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanum, Rorippa, Rotala, Lindernia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis, Papaver, Centaurea.
• Dicotyle Kulturen der Gattungen:
  Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cucumis, Cuburbita.
• Monokotyle Unkräuter der Gattungen:
  Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum, Sphenoclea, Dactyloctenium, Agrostis, Alopecurus, Apera.
• Monokotyle Kulturen der Gattungen:
  Oryza, Zea, Triticum, Rordeum, Avena, Secale, Sorghum, Panicum, Saccharum, Ananas, Asparagus, Allium.

The active compounds according to the invention can, for. B. can be used in the following plants:

• Dicotyledon weeds of the genera:
  Sinapis, Lepidium, Galium, Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanum, Rorippernia, Rorippa Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis, Papaver, Centaurea.
• Dicotyle cultures of the genera:
  Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cucumis, Cuburbita.
• Monocot weeds of the genera:
  Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleocharis, Scirpus, Paspalum, Spochhenium, Ischatenumum, Ischaeaeaum Agrostis, Alopecurus, Apera.
• Monocot cultures of the genera:
  Oryza, Zea, Triticum, Rordeum, Avena, Secale, Sorghum, Panicum, Saccharum, Pineapple, Asparagus, Allium.

However, the use of the active compounds according to the invention is by no means restricted to these genera, but extends in the same way to other plants.

The compounds are suitable for total weed control, depending on the concentration. B. on industrial and track systems and on paths and squares with and without tree cover. Likewise, the compounds for weed control in permanent crops, for. B. forest, ornamental wood, fruit, wine, citrus, nut, banana, coffee, tea, rubber, oil palm, cocoa, berry fruit and hop plants and used for selective weed control in annual crops will.

In addition to a very good action against grass-like weeds and against Cyperus species, the active compounds according to the invention also show a good herbicidal action in broad-leafed weeds. A selective use of the active ingredients according to the invention is possible, preferably in cereals, cotton and sugar beets, or in other crops.

The active compounds can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusts, pastes, soluble powders, granules, suspension emulsion concentrates, active substance-impregnated natural and synthetic substances, very fine encapsulations in polymeric substances.

These formulations are prepared in a known manner, e.g. B. by mixing the active ingredients with extenders, ie liquid solvents, and / or solid carriers, optionally using surface-active agents, ie emulsifiers and / or dispersants and / or foam-generating agents. In the case of the use of water as an extender, e.g. B. organic solvents can also be used as auxiliary solvents. The following are essentially suitable as liquid solvents: aromatics, such as xylene, toluene, or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzene, chloroethylene or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, e.g. B. petroleum fractions, alcohols, such as butanol or Glycoi and their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strong polar solvents such as dimethylformamide and dimethyl sulfoxide, and water.

As solid carriers come into question: B. natural rock powders such as kaolins, clays, talc, chalk, quartz, attapilgite, montmorillonite or diatomaceous earth and synthetic rock powders such as highly disperse silica, aluminum oxide and silicates; as solid carriers for granules come into question: z. B. broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite as well as synthetic granules from inorganic and organic flours as well as granules from organic material such as sawdust coconut shells, corn cobs and tobacco stalks; as emulsifying and / or foam-generating agents come into question: z. B. nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. B. alkylaryl polyglycol ether, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates; as dispersants come into question: z. B. lignin sulfite and methyl cellulose.

Adhesives such as carboxymethyl cellulose, natural and synthetic powdery, granular or latex-shaped polymers, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, can be used in the formulations.

Dyes such as inorganic pigments, e.g. B. iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc can be used.

The formulations generally contain between 0.1 and 95 percent by weight of active compound, preferably between 0.5 and 90%.

The active compounds according to the invention, as such or in their formulations, can also be used in a mixture with known herbicides for weed control, finished formulation or tank mixing being possible. A mixture with other known active compounds, such as fungicides, insecticides, acaricides, nematicides, bird repellants, growth agents, plant nutrients and agents which improve soil structure, is also possible.

The active compounds can be used as such, in the form of their formulations or in the use forms prepared therefrom by further dilution, such as ready-to-use solutions, suspensions, emulsions, powders, pastes and granules. The application happens in the usual way, e.g. B. by pouring, spraying, spraying, scattering.

The active compounds according to the invention can be applied both before and after emergence of the plants. It is preferably used before the plants emerge, that is to say in the pre-emergence process. They can also be worked into the soil before sowing.

The amount of active ingredient used can fluctuate in larger areas. It essentially depends on the type of effect you want. In general, the application rates are between 0.1 and 10 kg of active ingredient per ha, preferably between 0.1 and 5 kg / ha.

The active compounds according to the invention show growth-regulating properties when used after-run.

Example A shows the effects and possible uses for weed control.

2,6-Diethyl-N-methoxymethyl-chloracetanilidIn the example below, the compound specified below is used as the reference substance:

2,6-diethyl-N-methoxymethylchloroacetanilide

Example A Pre-emergence test

Solvent: 5 parts by weight of acetone

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.

• 0% = keine Wirkung (wie unbehandelte Kontrolle)
• 100% = totale Vernichtung

Seeds of the test plants are sown in normal soil and watered with the active compound preparation after 24 hours. The amount of water per unit area is expediently kept constant. The concentration of active substance in the preparation is irrelevant, the only decisive factor is the amount of active substance applied per unit area. After three weeks, the degree of damage to the plants is rated in% damage compared to the development of the untreated control. It means:

• 0% = no effect (like untreated control)
• 100% = total annihilation

Active ingredients, application rates and results are determined.

In this test, the active ingredient of Example 1 according to the invention shows a better selective activity than the substance (A) known from the prior art.

Manufacturing examples

A mixture of 14.1 g (0.05 mol) of 2,6-diethyl-N- (2'-oxo) propyl chloroacetanilide, 4.2 g (0.05 mol) of O-methyl-hydroxylammonium chloride and 7 g (0.05 mol) of powdered potassium carbonate is stirred at 20 ° C for 24 hours. The reaction mixture is then concentrated by distilling off the solvent in vacuo. The residue is partitioned between water and methylene chloride, the organic phase is separated off, dried over sodium sulfate and concentrated. The crystalline residue is recrystallized from petroleum ether at -10 ° C. 8.5 g (56% of theory) of 2,6-diethyl-N- (2'-methoxyimino) propyl chloroacetanilide of melting point 56-57 are obtained ° C.

Production of the preliminary stages

(Method (g) variant (ß))

39.5 g (0.15 mol) of 2,6-diethyl-N-propargylchloroacetanilide are added in portions at 80 ° C. in 85% formic acid. After stirring for two hours at 80 ° C., the reaction mixture is poured onto saturated amone sulfate solution, etherified and neutralized with sodium carbonate. After drying over sodium sulfate, the mixture is concentrated in vacuo and the residue is crystallized by rubbing with petroleum ether. 35.7 g (85% of theory) of 2,6-diethyl-N- (2'-oxo) propyl chloroacetanilide with a melting point of 65-67 ° C. are obtained.

112.7 g (0.5 mol) of 2,6-diethyl-chloroacetanilide are quickly mixed in a two-phase mixture of 500 ml of methylene chloride and 250 ml of 50% sodium hydroxide solution / water after adding 1.5 g of triethylbenzylammonium chloride (TEBA) stirred and 59.5 g (0.5 mol) of propargyl bromide was added dropwise at 25-35 ° C. The mixture is stirred for a further four hours at 20 ° C., the organic phase is separated off, washed several times with water, dried over sodium sulfate and concentrated in vacuo. The residue is recrystallized from isopropanol. 67.8 g (51.5% of theory) of 2,6-diethyl-N-propargylchloroacetanilide with a melting point of 57-58 ° C. are obtained.

Example 2

(Method (a))

6 g (0.03 mol) of 2.6 dimethyl-N (2 'methoxyimino-ethyl) aniline and 2.8 g (0.035 mol) of pyridine are boiled in 80 ml of anhydrous fetrahydrofuran and mixed with 4 g (0.035 mol) Chloroacetyl chloride is added after 15 minutes of heating under reflux, the reaction mixture is cooled and concentrated in vacuo. The residue is partitioned between water and methylene chlorof, the organic phase is separated off, dried over sodium sulfate and concentrated. The oily residue crystallizes after treatment with petroleum ether. 4.8 g (60% of theory) of 2.6 dimethyl N (2'-methoxyiminoethyl) chloroacetanilide with a melting point of 56-58 ° C. are obtained.

Manufacture of the starting product

(Method (s), variant (\))

48.4 g (0.4 mol) of 2.6 dimethylaniline and 27.6 g (0.2 mol) of finely powdered potassium carbonate are heated in 80 ml of dimethylformamide with stirring to 100 ° C. and added dropwise with 21.5 g (0.05 2 mol) of chloroacetaldehyde-O methyl oxime ether were added. After stirring for 3 hours at 100 ° C, the inorganic salt is filtered off. The filtrate is mixed with 250 ml of methylene chloride, shaken out several times with water, dried over sodium sulfate and concentrated in vacuo. The residue is distilled. 14.2 g (37% of theory) of 2,6-dimethyl N- (2'-methoxy-imino-ethyl) -aniline having a boiling point of 105-110 ° C./0.133 mbar and a refractive index n of 1.537 are obtained

Example 3

(Method (a))

13.4 g (0.05 mol) of \ (2,6-dimethylphenylamino) acetophenone oxime-O-methyl ether are dissolved in 200 ml of toluene, mixed with 4 ml (0.05 mol) of chloroacetyl chloride and 6 hours to the end Gas de-heating heated under reflux. Allow to cool and concentrate by distilling off the Solvent in a vacuum. The residue is purified by chromatography. 3.1 g (18% of theory) of x- [2.6 dimethylphenyl) -N chloroacetylamino] -acetophenone oxime () methyl ether of melting point 80 ° C. are obtained.

Production of the preliminary stages

(Method (f))

3 ¹ , 2 g (0.11 mol) \ (2,6-dimethylphenylamino) acetophenone oxime hydrochloride and 0.6 g (0.176 mol) benzyldimethylammonium chloride are dissolved in 110 ml methylene chloride and after adding 110 ml concentrated sodium hydroxide solution and 6.9 g (0.055 mol) of dimethyl sulfate 6 stirred at 20 c. After pouring on ice, the organic phase is separated off, washed with water, dried over sodium sulfate and evaporated. 25.7 g (87% of theory) of α- (2,6-dimethylphenylamino) -ace tophenonoxime O methyl ether of refractive index n: 1.5877 are obtained.

(Method (s) variant (γ))

59.7 g (0.3 mol) of phenacyl bromide (for preparation see Org. Syntheses Vol. II, p. 480) and 13.2 g (0.6 mol) of 2,6-dimethylaniline are dissolved in 100 ml of ethyl alcohol for 10 minutes Heated 80 ° C and then concentrated in vacuo. The residue is taken up in toluene and filtered. The filtrate is diluted with ethyl alcohol and 20.8 g (0.165 mol) of hydroxylammonium chloride and 22.6 g (0.165 mol) of powdered potassium carbonate are added. After stirring for 20 hours at room temperature, the mixture is filtered and the filtrate is concentrated. The residue is crystallized by trituration with a little ethyl alcohol. 33.9 g (40% of theory) of α- (2,6-dimethylphenylamino) acetophenonoxime hydrochloride with a melting point of 200 ° C. are obtained.

According to one or more of the processes described in the application and in accordance with Examples 1 to 3, the compounds of the formula (I) according to the invention which are listed in Table 1 below are obtained.

According to one or more of the processes described in the application and in accordance with Examples 2 and 3, the starting products of the formula (II) listed in Table 2 below are obtained

According to one or more of the processes described in the application and in accordance with Example 1, the starting products of the formula (VI) listed in Table 3 below are obtained.

Claims (6)

1. Oxime ethers of the formula

in which

R' represents hydrogen, alkyl or alkoxy,

R² represents hydrogen, alkyl, alkoxy or halogen,

R³ represents hydrogen, alkyl, alkoxy or halogen,

R⁴ represents hydrogen or alkyl,

R⁵ represents hydrogen, alkyl or optionally substituted aryl, R⁶ represents hydrogen, alkyl, alkenyl, alkinyl, alkoxyalkyl, alkylthioalkyl, dialkylaminoalkyl, halogenoalkyl, alkoxycarbonylalkyl, optionally substituted aryl or optionally substituted aralkyl, and in addition

R⁵ and R⁶ together represent an alkylene group, and

Z represents halogen.

2. Process for the preparation of oxime ethers of the formula

in which

R' represents hydrogen, alkyl or alkoxy,

R² represents hydrogen, alkyl, alkoxy or halogen,

R³ represents hydrogen, alkyl, alkoxy or halogen,

R⁴ represents hydrogen or alkyl,

R⁵ represents hydrogen, alkyl or optionally substituted aryl,

R⁶ represents hydrogen, alkyl, alkenyl, alkinyl, alkoxyalkyl, alkylthioalkyl, dialkylaminoalkyl, halogenoalkyl, alkoxycarbonylalkyl, optionally substituted aryl or optionally substituted aralkyl, and in addition

R⁵ and R⁶ together represent an alkylene group, and

Z represents halogen,

characterised in that

a) anilinomethyl oxime ethers of the formula

in which

R¹, R², R³, R4, R⁵ and R6 have the meaning indicated above,

are reacted with halogenoacetic acid chlorides or bromides or anhydrides of the formulae

or

in which

Z has the meaning indicated above,

in the presence of a diluent and if appropriate in the presence of an acid-binding agent, or

b) halogenoacetanilides of the formula

in which

R¹, R², R³ and Z have the meaning indicated above, are reacted with substituted oxime ethers of the formula

in which

R4, R5 and R⁶ have the meaning indicated above and

Y represents halogen or the mesylate or tosylate radical,

in the presence of an acid-binding agent and if appropriate in the presence of a diluent, or

c) N-substituted halogenoacetanilides of the formula

in which

R', R2, R3, R⁴, R⁵ and Z have the meaning indicated above,

are reacted with salts of hydroxylamine (derivatives) of the formula

in which

R⁶ has the meaning indicated above,

in the presence of a diluent and in the presence of an acidbinding agent, or

d) alkali metal salts of oximes of the formula

in which

R', R², R³, R⁴, R⁵ and Z have the meaning indicated above,

are reacted with halides of the formula

in which

R⁷ represents alkyl, alkenyl, alkinyl, alkoxyalkyl, alkylthioalkyl, dialkylaminoalkyl, halogenoalkyl, alkoxycarbonylalkyl, optionally substituted aryl or optionally substituted aralkyl and

X represents chlorineor bromine,

in the presence of an organic diluent or in the presence of an organic-inorganic two-phase system in the presence of a phase transfer catalyst, the alkali metal salts of the oximes of the formula (VIII) being produced in situ.

3. Herbicidal agents, characterised in that they contain at least one oxime ether of the formula (I) according to Claim 1.

4. Process for combating weeds, characterised in that oxime ethers of the formula (I) according to Claim 1 are allowed to act on weeds and/or their environment.

5. Use of oxime ethers of the formula (I) according to Claim 1 for combating weeds.

6. Process for the preparation of herbicidal agents, charactensed in that oxime ethers of the formula (I) according to Claim 1 are mixed with extenders and/or surface-active substances.